CN114450325A

CN114450325A - Fluorine-containing ether compound, surface treatment agent, fluorine-containing ether composition, coating liquid, article, and compound

Info

Publication number: CN114450325A
Application number: CN202080065686.6A
Authority: CN
Inventors: 高下隆太
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2019-09-20
Filing date: 2020-09-17
Publication date: 2022-05-06
Also published as: US20220213345A1; EP4032933A1; EP4032933A4; TW202124522A; WO2021054413A1; KR20220066125A; JPWO2021054413A1

Abstract

Providing: a fluorine-containing ether compound capable of forming a surface layer having excellent durability, a fluorine-containing ether composition and a coating liquid, an article having a surface layer having excellent durability, and a compound useful as a raw material for a fluorine-containing ether compound. A fluorine-containing ether compound represented by the following formula (A1) or formula (A2). R^f‑O‑(R^f1O)_m‑R^f2[‑R¹‑C(‑R²‑T)_a(‑R³)_3‑a]_bFormula (A1) [ (T-R)²‑)_a(R³‑)_3‑aC‑R¹‑]_bR^f2‑O‑(R^f1O)_m‑R^f2[‑R¹‑C(‑R²‑T)_a(‑R³)_3‑a]_bIn the formula (A2), the symbols in the formula are as defined in the specification.

Description

Fluorine-containing ether compound, surface treatment agent, fluorine-containing ether composition, coating liquid, article, and compound

Technical Field

The present invention relates to a fluorinated ether compound, a surface treatment agent, a fluorinated ether composition, a coating liquid, an article, and a compound.

Background

The fluorine-containing ether compound having a perfluoropolyether chain and a hydrolyzable silyl group is suitable for use as a surface treatment agent because it can form a surface layer exhibiting high lubricity, water/oil repellency, and the like on the surface of a substrate. Use of a surface treatment agent comprising a fluorine-containing ether compound for applications requiring maintenance of the following properties for a long period of time: the surface layer is repeatedly rubbed with a finger, and is used as a surface treatment agent for a member constituting a surface of a touch panel to be contacted with a finger, a spectacle lens, and a display of a wearable terminal, for example, because the surface layer is not easily degraded in water-and oil-repellency (rubbing resistance) and the surface layer is easily wiped to remove a fingerprint attached to the surface layer (fingerprint stain removing property).

As a fluorine-containing ether compound capable of forming a surface layer excellent in abrasion resistance and fingerprint stain removability on the surface of a base material, a fluorine-containing ether compound having a perfluoropolyether chain and a hydrolyzable silyl group has been proposed (patent documents 1 to 3).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2016-037541

Patent document 2: international publication No. 2017/022437

Patent document 3: international publication No. 2017/038830

Disclosure of Invention

Problems to be solved by the invention

The surface treatment agent can be used not only for a display surface of a smartphone, a tablet terminal, or the like, but also for surface treatment of a back surface (a surface opposite to a display screen) of a mobile device in some cases. Further improvement in durability of the surface treatment agent is demanded.

An object of the present invention is to provide: a fluorine-containing ether compound capable of forming a surface layer having excellent durability, a surface treatment agent, a fluorine-containing ether composition, and a coating liquid each containing the fluorine-containing ether compound, an article having a surface layer having excellent durability, and a compound useful as a raw material for a fluorine-containing ether compound.

Means for solving the problems

The present invention provides: a fluorine-containing ether compound having the following configurations [1] to [13], a surface treatment agent, a fluorine-containing ether composition, a coating liquid, an article, and a raw material compound of a fluorine-containing compound.

[1] A fluorine-containing ether compound represented by the following formula (A1) or formula (A2).

R^f-O-(R^f1O)_m-R^f2[-R¹-C(-R²-T)_a(-R³)_3-a]_bFormula (A1)

[(T-R²-)_a(R³-)_3-aC-R¹-]_bR^f2-O-(R^f1O)_m-R^f2[-R¹-C(-R²-T)_a(-R³)_3-a]_bFormula (A2)

Wherein, the first and the second end of the pipe are connected with each other,

R^fis a fluoroalkyl group having 1 to 20 carbon atoms,

R^f1a C1-C6 fluoroalkylene group,

R^f2an organic radical having a valence of (1+ b), at least between R¹The bound carbon atoms having fluorine atoms, R^f2In the case of plural, the R^f2Optionally the same or different, and optionally,

R¹is C1-20 alkylene, R¹In the case of plural, the R¹Optionally the same or different, and optionally,

R²is C2-C10 alkylene optionally having fluorine atom, multiple R²Optionally the same or different, and optionally,

R³is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and optionally having a fluorine atom, R³When there are plural, the plural R³Optionally the same or different, and optionally,

t is-Si (R)_3-c(L)_cAnd a plurality of T are optionally the same or different,

r is an alkyl group, and R is a substituted alkyl group,

l is a hydrolyzable group or a hydroxyl group, and at least 2 of L in T are the same or different,

m is an integer of 1 to 20,

a is an integer of 1 to 3, and when a plurality of a's are present, a plurality of a's are optionally the same or different,

b is an integer of 1 or more, and when there are a plurality of b, the plurality of b are optionally the same or different,

c is 2 or 3, a plurality of c are optionally the same or different,

when b is 1, a is 2 or 3.

[2]According to [1]Wherein a plurality of R are present²All of the carbon numbers of (2) are 3 or more.

[3]According to [1]Or [ 2]]Wherein R is¹The number of carbon atoms of (2) is 5 to 20.

[4]According to [1]～[3]wherein-CH is₂-in an amount of 8 to 30.

[5] The fluorine-containing ether compounds according to [1] to [4], wherein the weight average molecular weight (Mw)/number average molecular weight (Mn) is 1.2 or less.

[6] The fluorine-containing ether compound according to any one of [1] to [5], wherein the hydrolyzable group is an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, or an isocyanate group.

[7] A surface treatment agent comprising the compounds of [1] to [6 ].

[8] A fluoroether composition comprising: a fluorine-containing ether compound represented by the following formula (A1) and a fluorine-containing ether compound represented by the following formula (A2).

R^f-O-(R^f1O)_m-R^f2[-R¹-C(-R²-T)_a(-R³)_3-a]_bFormula (A1)

Wherein the content of the first and second substances,

R^fis a fluoroalkyl group having 1 to 20 carbon atoms,

R^f1a C1-C6 fluoroalkylene group,

R^f2an organic radical having a valence of (1+ b), at least between R¹The bound carbon atom having a fluorine atom, R^f2In the case of plural, the R^f2Optionally the same or different, and optionally,

t is-Si (R)_3-c(L)_cAnd a plurality of T are optionally the same or different,

r is an alkyl group, and R is a substituted alkyl group,

m is an integer of 1 to 20,

c is 2 or 3, a plurality of c are optionally the same or different,

when b is 1, a is 2 or 3.

[9] A fluoroether composition comprising: 1 or more kinds of the fluorine-containing ether compounds of [1] to [6], and other fluorine-containing ether compounds.

[10] A coating liquid containing the fluorine-containing ether compound of [1] to [6] or the fluorine-containing ether composition of [8] or [9],

and contains a liquid medium.

[11] An article having a surface layer on the surface of a substrate, wherein the surface layer is formed from a fluorine-containing ether compound of [1] to [6] or a fluorine-containing ether composition of [8] or [9 ].

[12] A compound represented by the following formula (B1).

(CH₂＝CH-R²⁰-)_a(R³-)_3-aC-R²¹-X formula (B1)

Wherein the content of the first and second substances,

R²⁰is a single bond or C1-C8 alkylene optionally having a fluorine atom, R²⁰When there are plural, the plural R²⁰Optionally the same or different, and optionally,

R²¹a single bond or an alkylene group having 1 to 19 carbon atoms,

x is a chlorine atom, a bromine atom, or an iodine atom,

a is an integer of 1 to 3.

[13] A compound represented by the following formula (B2).

(CH₂＝CH-R²⁰-)_a(R³-)_3-aC-R²¹-MgX formula (B2)

Wherein the content of the first and second substances,

R²¹a single bond or an alkylene group having 1 to 19 carbon atoms,

x is a chlorine atom, a bromine atom, or an iodine atom,

a is an integer of 1 to 3.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there is provided: a fluorine-containing ether compound capable of forming a surface layer having excellent durability, a surface treatment agent, a fluorine-containing ether composition, and a coating liquid each containing the fluorine-containing ether compound, an article having a surface layer having excellent durability, and a compound useful as a raw material for a fluorine-containing ether compound.

Detailed Description

In the present specification, the compound represented by the formula (a1) is referred to as compound (a 1). Other compounds represented by the formulae and the like are also based on these.

The following terms in the present specification have the meanings as described below.

"reactive silyl group" is a generic name for a hydrolyzable silyl group and a silanol group (Si-OH). Reactive silyl is, for example, T, i.e., -Si (R) in the formula (A1) or the formula (A2)_3-c(L)_c。

The "hydrolyzable silyl group" refers to a group which undergoes a hydrolysis reaction to form a silanol group.

The "surface layer" refers to a layer formed on the surface of the substrate.

When the fluorine-containing ether compound is a mixture of a plurality of fluorine-containing ether compounds having different chain lengths of the polyfluoropolyether chain, the "molecular weight" of the polyfluoropolyether chain is determined based on¹H-NMR and¹⁹F-NMR was carried out by obtaining the number average molecular weight calculated by taking the number (average value) of the oxyfluoroalkylene units based on the terminal group. The terminal group is, for example, R in the formula (A1)^fOr T in formula (A1) or formula (A2).

In the case where the fluorine-containing ether compound is a fluorine-containing ether compound in which the chain length of the polyfluoropolyether chain is single, the "molecular weight" of the polyfluoropolyether chain is determined based on¹H-NMR and¹⁹F-NMR, determination of R^fMolecular weight calculated from the structure of (1).

"to" indicating a numerical range includes the numerical values described before and after the range as the lower limit and the upper limit.

[ fluorine-containing ether Compound ]

The fluorine-containing ether compound of the present invention (hereinafter also referred to as "the present compound") is a fluorine-containing ether compound represented by the following formula (a1) or formula (a 2).

R^f-O-(R^f1O)_m-R^f2[-R¹-C(-R²-T)_a(-R³)_3-a]_bFormula (A1)

Wherein the content of the first and second substances,

R^fis a fluoroalkyl group having 1 to 20 carbon atoms,

R^f1a C1-C6 fluoroalkylene group,

t is-Si (R)_3-c(L)_cAnd a plurality of T are optionally the same or different,

r is an alkyl group, and R is a substituted alkyl group,

m is an integer of 1 to 20,

c is 2 or 3, a plurality of c are optionally the same or different,

when b is 1, a is 2 or 3.

The present compound described above has: polyfluoropolyether chain [ R ]^f-O-(R^f1O)_m-]Or [ -O- (R)^f1O)_m-]Reactive silyl group, and specific linking group-R for linking polyfluoropolyether chain and reactive silyl group^f2[-R¹-C(-R²-)_a]_b。

The compound (A1) is a compound having a structure of "1-valent polyfluoropolyether chain-linking group-reactive silyl group", and the compound (A2) is a compound having a structure of "reactive silyl group-linking group-2-valent polyfluoropolyether chain-linking group-reactive silyl group".

The compound has a polyfluoropolyether chain. The fingerprint stain removability of the surface layer of the present compound having a polyfluoropolyether chain is excellent. In addition, the present compound has a reactive silyl group at least at one terminal. The present compound having a reactive silyl group at the terminal is strongly chemically bonded to the base material, and therefore, the surface layer has excellent abrasion resistance. Further, in the present compound, the linking group is composed of a carbon chain having no ether bond (-C-O-C-). Therefore, chemical stability is improved for the linking group containing an ether bond, which has been widely used conventionally. As a result, the surface layer formed of the present compound has excellent durability such as abrasion resistance, chemical resistance, and light resistance. The present compound is suitably used as a surface treatment agent because it can form a surface layer exhibiting such high lubricity, water/oil repellency, and the like on the surface of a substrate.

R^fThe fluoroalkyl group having 1 to 20 carbon atoms further excels in the abrasion resistance of the surface layer and the removal of fingerprint contaminants. R is more excellent in the abrasion resistance of the surface layer and the removal of fingerprint contaminants^fThe number of carbon atoms of the fluoroalkyl group(s) is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 to 3.

As R^fThe fluoroalkyl group (b) is preferably a perfluoroalkyl group, because the surface layer is further excellent in abrasion resistance and fingerprint contaminant removal property. R^fThe compound being perfluoroalkyl has CF at the end₃-. According to end being CF₃The compound of (a) can form a surface layer having a low surface energy, and therefore, the rubbing resistance and fingerprint contaminant removal property of the surface layer are further excellent.

As R^fThe fluoroalkyl group of (A) includes, for example, CF₃-、CF₃CF₂-、CF₃CF₂CF₂-、CF₃CF₂CF₂CF₂-、CF₃CF₂CF₂CF₂CF₂-、CF₃CF₂CF₂CF₂CF₂CF₂-、CF₃CF(CF₃) -and the like.

As (R)^f1O)_mFrom the viewpoint that the abrasion resistance of the surface layer and the fingerprint stain removability are further excellent, the following formula (R) is preferable^f1-1) the structure shown.

(R^f11O)_m1(R^f12O)_m2(R^f13O)_m3(R^f14O)_m4(R^f15O)_m5(R^f16O)_m6Formula (R)^f1-1)

Wherein the content of the first and second substances,

R^f11is a C1 fluoroalkylene group,

R^f12is a C2 fluoroalkylene group,

R^f13is a C3 fluoroalkylene group,

R^f14is a C4 fluoroalkylene group,

R^f15is a C5 fluoroalkylene group,

R^f16is a C6 fluoroalkylene group,

m1, m2, m3, m4, m5 and m6 independently represent an integer of 0 or 1 or more, m1+ m2+ m3+ m4+ m5+ m6 are integers of 1 to 200, and R is^f11～R^f16When there are plural, the plural R^f11～R^f16Optionally the same or different.

Wherein R is represented by the formula^f1(R) in (1)^f11O)～(R^f16O) is arbitrary. Formula (R)^f1M1 to m6 of-1) each represents (R)^f11O)～(R^f16O) does not indicate a configuration. For example, (R)^f15O)_m5Is represented by (R)^f15O) is m5, not representing (R)^f5O)_m5Block configuration structure of (2). Likewise, (R)^f11O)～(R^f16O) does not indicate the combination of the respective unitsAnd (4) sequencing.

The fluoroalkylene group having 3 to 6 carbon atoms may be a linear fluoroalkylene group, or a fluoroalkylene group having a branched or cyclic structure.

As R^f11Specific examples of (3) include CHF and CF₂. As R^f12Specific examples of (3) include CF₂CF₂、CF₂CHF、CF₂CH₂And the like. As R^f13Specific examples of (3) include CF₂CF₂CF₂、CF₂CF₂CHF、CF₂CHFCF₂、CF₂CF₂CH₂、CF₂CH₂CF₂、CF(CF₃)CF₂And the like. As R^f14Specific examples of (3) include CF₂CF₂CF₂CF₂、CF₂CF₂CF₂CH₂、CHFCF₂CF₂CF₂、CF₂CH₂CF₂CF₂、CF(CF₃)CF₂CF₂Perfluorocyclobutane-1, 2-diyl, and the like. As R^f15Specific examples of (3) include CF₂CF₂CF₂CF₂CF₂、CF₂CF₂CF₂CF₂CH₂、CHFCF₂CF₂CF₂CF₂、CF₂CF₂CH₂CF₂CF₂And the like. As R^f16Specific examples of (3) include CF₂CF₂CF₂CF₂CF₂CF₂、CF₂CF₂CF₂CF₂CF₂CH₂、CF₂CF₂CF₂CF₂CF₂CHF, and the like.

R^f2An organic radical having a valence of (1+ b), at least at the position corresponding to R¹The bonded carbon atoms have fluorine atoms. Namely, R^f2Is a compound having b partial structures "-CQF- (wherein Q is a hydrogen atom or a fluorine atom-) and R¹Bonded atomic bonds. ) "or" an organic group. R^f2The carbon number of (C) is preferably 1 to 6. Examples of the organic group includeA hydrocarbon group optionally having a substituent is produced. Examples of the hydrocarbon group include a linear or branched alkyl group, a cycloalkyl group, an aryl group, and a combination thereof. The hydrocarbyl group may have a double or triple bond in the carbon chain. Examples of the combination include a combination in which an alkyl group is bonded to an aryl group, and a combination in which an alkyl group is bonded to a cycloalkyl group.

The substituent optionally contained in the hydrocarbon group is preferably a halogen atom, and among them, a fluorine atom is more preferable. In view of ease of production, b is preferably 1 to 10, more preferably 1 to 6.

When b is 1, R^f2Is a 2-valent group. As R in this case^f2Examples thereof include: optionally substituted, fluoroalkylene optionally having a bond in the carbon chain other than heteroatom or (fluoro) alkylene. In view of durability of the present compound, R when b is 1^f2Preferably a C1-C6 fluoroalkylene group. As R in this case^f2Specific examples of (B) include-CHF-, -CF₂-*、CF₂CF₂-*、CF₂CHF-*、CH₂CF₂-*、CF₂CF₂CF₂-*、CF₂CF₂CHF-*、CF₂CHFCF₂-*、CH₂CF₂CF₂-*、CF₂CH₂CF₂-*、CF(CF₃)CF₂-*、CF₂CF₂CF₂CF₂-*、CH₂CF₂CF₂CF₂-*、CHFCF₂CF₂CF₂-*、CF₂CH₂CF₂CF₂-*、CF(CF₃)CF₂CF₂-*、CF₂CF₂CF₂CF₂CF₂-*、CH₂CF₂CF₂CF₂CF₂-*、CHFCF₂CF₂CF₂CF₂-*、CF₂CF₂CH₂CF₂CF₂-*、CF₂CF₂CF₂CF₂CF₂CF₂-*、CH₂CF₂CF₂CF₂CF₂CF₂-*、CF₂CF₂CF₂CF₂CF₂CHF-, etc.

When b is 2 or more, R^f2Is 1 or more (1+ b) -valent groups having a branch point P selected from tertiary carbon atoms, quaternary carbon atoms, and ring structures.

The carbon atom constituting the branch point is preferably a tertiary carbon atom or a quaternary carbon atom from the viewpoint of ease of production of the present compound and durability such as abrasion resistance, chemical resistance, and light resistance of the surface layer.

The ring structure constituting the branch point includes, from the viewpoint of ease of production of the present compound, durability such as abrasion resistance, chemical resistance, and light resistance of the surface layer, an aliphatic ring having 3 to 8 membered rings, an aromatic ring having 6 to 8 membered rings, a heterocyclic ring having 3 to 8 membered rings, and a condensed ring formed of 2 or more of these rings, and is preferably selected from among an aliphatic ring having 3 to 8 membered rings, an aromatic ring having 6 to 8 membered rings, and a ring structure in these condensed rings, from the viewpoint of durability such as abrasion resistance, chemical resistance, and light resistance of the surface layer. Examples of the ring structure constituting the branch point include ring structures represented by the following formula. The following ring structures are optionally substituted with fluorine atoms. The ring structure may have, as a substituent, an alkyl group, a cycloalkyl group, an alkenyl group, an allyl group, or the like, which may have a halogen atom.

As R^f2A combination of 2 or more fluoroalkylene groups having a valence of 2 and 1 or more branch points P is preferable.

Shown below as R^f2A preferable specific example when the valence is 3 or more. In the following formula, R represents^FIs represented by (R)^f1O)m，R^FAnd R¹Do not form R^f2。

R¹Is carbonA number of 1 to 20 alkylene groups. R¹Having no fluorine atoms. R¹By being an alkylene group having no ether bond, the durability of the surface layer and the fingerprint contaminant removability are further excellent. From the viewpoint that the durability of the surface layer and the removal property of fingerprint contaminants are further excellent, R¹The number of carbon atoms of (B) is preferably 5 to 20, more preferably 7 to 10. In addition, R is R in terms of abrasion resistance of the surface layer¹The number of carbons of (a) is preferably an odd number, more preferably 3, 5, 7 or 9.

R²Is an alkylene group having 2 to 10 carbon atoms and optionally having a fluorine atom. R²By being an alkylene group having no ether bond, the durability of the surface layer and the fingerprint contaminant removability are further excellent. From the viewpoint that the durability of the surface layer and the removal property of fingerprint contaminants are further excellent, R²The carbon number of (C) is preferably 3 to 10. From the viewpoint of further excellent durability of the surface layer and removal of fingerprint contaminants, a plurality of R's are preferable²At least one of R is 3 or more, preferably a plurality of R²All of the carbon numbers of (2) are 3 or more. In addition, R is R in terms of durability of the surface layer and the like²Alkylene groups having no fluorine atom are preferred.

Further, in the present compound, "-CH" in the molecule₂The number of-atoms, i.e., the number of carbon atoms not bonded to a fluorine atom is preferably 8 to 30, preferably 10 to 20. In particular, R¹And R²of-CH contained in₂The total of-is preferably 8 to 30, preferably 10 to 20. The durability of the surface layer of this compound and the fingerprint contaminant removal property are further excellent.

R³Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and optionally having a fluorine atom. R³By being a hydrogen atom, or an alkyl group optionally having a fluorine atom, the durability of the surface layer and the fingerprint contaminant removability are further excellent. From the viewpoint that the durability of the surface layer and the removal property of fingerprint contaminants are further excellent, R³Preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms and optionally having a fluorine atom, more preferably a hydrogen atom.

T is-Si (R)_3-c(L)_cIs a reactive silyl group.

The reactive silyl group is a group in which either or both of a hydrolyzable group and a hydroxyl group are bonded to a silicon atom.

The hydrolyzable group is a group that becomes a hydroxyl group by a hydrolysis reaction. That is, the hydrolyzable silyl group becomes a silanol group (Si — OH) by a hydrolysis reaction. The silanol group further undergoes a dehydration condensation reaction between molecules to form an Si-O-Si bond. In addition, the silanol group and the hydroxyl group on the surface of the substrate (substrate-OH) undergo a dehydration condensation reaction to form a chemical bond (substrate-O-Si).

Examples of the hydrolyzable group include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanate group. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. The halogen atom is preferably a chlorine atom. The acyl group is preferably an acyl group having 1 to 6 carbon atoms. The acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms.

The hydrolyzable group is preferably an alkoxy group or a halogen atom, because the compound can be easily produced. The hydrolyzable group is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint of less outgassing at the time of coating and excellent storage stability of the present compound, and particularly preferably an ethoxy group when long-term storage stability of the present compound is required, and particularly preferably a methoxy group when the reaction time after coating is short.

The number of carbon atoms of the alkyl group in R is preferably 1 to 6, more preferably 1 to 3, particularly preferably 1 to 2, from the viewpoint of ease of production of the present compound.

C is preferably 2 or 3, more preferably 3, from the viewpoint of more firm adhesion between the surface layer and the base material.

The plurality of T are optionally the same or different. From the viewpoint of ease of production of the present compound, it is preferable that T be the same group.

In addition, from the viewpoint of durability of the surface layer, it is preferable that 2 or more T are arranged at each end, and from this viewpoint, when b is 1, a is 2 or 3.

Examples of the present compound include compounds of the following formula. The compound of the following formula is further excellent in water-and oil-repellency of the surface layer, abrasion resistance, fingerprint contaminant removal property, lubricity, chemical resistance, light resistance and chemical resistance, and is easy to industrially produce and handle. In addition, from the viewpoint of durability, the present compound preferably has a weight average molecular weight (Mw)/number average molecular weight (Mn) of 1.2 or less.

In the formula, x1 to x16 are each independently an integer of 1 to 100, and y1 to y7 are each independently an integer of 1 to 7.

(Process for producing Compound (A1) and Compound (A2))

The compound (a1) can be produced, for example, by a method in which the following compound (a11) and the compound (1a) are subjected to a hydrosilylation reaction. The compound (a2) can be produced, for example, by a method in which the following compound (a21) and the compound (1a) are subjected to a hydrosilylation reaction.

R^f-O-(R^f1O)_m-R^f2[-R¹-C(-R²⁰-CH＝CH₂)_a(-R³)_3-a]_bFormula (A11)

[(CH₂＝CH-R²⁰-)_a(R³-)_3-aC-R¹-]_bR^f2-O-(R^f1O)_m-R^f2[-R¹-C(-R²⁰-CH＝CH₂)_a(-R³)_3-a]_bFormula (A21)

HSi(R)_3-c(L)_cFormula (1a)

Wherein R in the formula²⁰Is a single bond or C1-C8 alkylene optionally having a fluorine atom, except R²⁰The other symbols are the same as those in the above formula (A1) or formula (A2).

-R²⁰-CH＝CH₂After hydrosilylation to R². As R²⁰Examples thereof include²The same applies to the same groups, as to the preferred embodiments.

(Process for producing Compound (A11) and Compound (A21))

The compound (a11) can be produced, for example, by a method in which the following compound (a12) is reacted with the following compound (B2). The compound (a21) can be produced, for example, by a method in which the following compound (a22) is reacted with the following compound (B2).

R^f-O-(R^f1O)_m-R^f2-CH₂-L²Formula (A12)

L²-CH₂-R^f2-O-(R^f1O)m-R^f2-CH₂-L²Formula (A22)

(CH₂＝CH-R²⁰-)_a(R³-)_3-aC-R²¹-MgX formula (B2)

Wherein the content of the first and second substances,

L²is a sulfonate group, and is a sulfonic acid ester group,

R²¹a single bond or an alkylene group having 1 to 19 carbon atoms,

x is a chlorine atom, a bromine atom, or an iodine atom,

the other symbols are the same as those in the aforementioned formula (A11) or formula (A21).

The sulfonate group of compound (a12) or compound (a12) and MgX of compound (B2) are reacted (grignard reaction) as in the following reaction scheme (1).

Reaction scheme (1)

-R^f2-CH₂-L²+XMg-R²¹-→-R^f2-CH₂-R²¹

Wherein each symbol in the reaction scheme (1) is as defined above.

Note that CH after the above reaction₂-R²¹Corresponding to R of the present compound¹。

L²Is sulfonate (-O-SO)₂-R²²) And removed by reaction with a grignard reagent. It should be noted that, in the following description,R²²is an organic group. By selecting a sulfonate group as L²Thus, the reaction of the reaction scheme (1) can be carried out under relatively mild conditions and in high yield.

Specific examples of the sulfonate group include tosylate group (OTs), mesylate group (OMs), triflate group (OTf), nonafluoromethanesulfonate group (ONf), and the like. Among them, the trifluoromethanesulfonate group is preferable from the viewpoint of the reaction yield in the reaction scheme (1).

The compound (a12) or the compound (a22) can be produced by a method in which a compound represented by the following compound (a13) or compound (a23) is reacted with trifluoromethanesulfonic anhydride, tosyl chloride, methanesulfonyl chloride, or the like in the presence of an organic amine compound such as triethylamine or pyridine, and the resulting product is subjected to sulfonation.

R^f-O-(R^f1O)_m-R^f2-CH₂-OH formula (A13)

L²-CH₂-R^f2-O-(R^f1O)_m-R^f2-CH₂-OH formula (A23)

Wherein A in the formula¹、A²And n is as previously described.

Compound (a13) and compound (a23) can be produced, for example, by referring to international publication No. 2017/038830 and the like.

The compound (B2) can be produced, for example, by a method in which the following compound (B1) is reacted with metallic magnesium.

(CH₂＝CH-R²⁰-)_a(R³-)_3-aC-R²¹-X formula (B1)

Wherein R in the formula²⁰、R²¹、R³X and a are the same as in compound (B2).

The compound (B1) can be obtained by, for example, halogenating a hydroxyl group of an unsaturated alcohol. The unsaturated alcohol may be synthesized or a commercially available product may be used.

Suitable specific examples of the compound (B2) include the following.

In the reaction of reaction scheme (1), the amount of the compound (B2) used is such that the sulfonate group L contained in the compound (a12) or the compound (a12) is higher than the sulfonate group L contained in the compound (a12) or the compound (a12) in order to improve the yield of the target compound²The total amount of (A) is preferably 1 to 30 equivalents, more preferably 3 to 20 equivalents, and still more preferably 5 to 15 equivalents.

In the reaction of the reaction scheme (1), a transition metal compound is preferably used as a catalyst from the viewpoint of improving the reactivity and achieving a high yield. The transition metal compound can be suitably selected from known catalysts used in the grignard reaction and used. The transition metal compound is preferably a compound containing an element of groups 3 to 12 of the periodic table as a transition metal, and particularly preferably a compound containing an element of groups 8 to 11. The group 8 to 11 element preferably contains 1 or more elements selected from copper, nickel, palladium, cobalt, and iron, and more preferably contains copper.

When the transition metal compound contains copper, the copper may be any of compounds having 0, 1,2 and 3 valences, and among them, a salt or complex salt of copper having 1 or 2 valences is preferable from the viewpoint of catalytic ability. Further, from the viewpoint of ease of obtaining, etc., copper chloride is more preferable.

The transition metal compound is used in an amount corresponding to the sulfonate group L²The total amount of (a) is, for example, 0.1 to 50 mol%, preferably 1 to 30 mol%, and more preferably 2 to 20 mol%.

The transition metal compound may be used in combination with a ligand. By using the ligand, the yield of the target product is improved. On the other hand, in the present production method, since a sufficient yield can be obtained without using a ligand, the ligand may not be used.

Examples of the ligand include 1, 3-butadiene, phenyl propyne, Tetramethylethylenediamine (TMEDA), and the like. When a ligand is used, the yield of the target compound is improved with respect to the sulfonate group L²The total amount of (A) is preferably 0.01 to 20 equivalents, more preferably 0.1 to 1.2 equivalents.

Moreover, the reaction of reaction scheme (1) is generally carried out in a solvent. The solvent can be suitably selected from solvents capable of dissolving the aforementioned compound (a12), compound (a13) and compound (B2) and used. The solvent may be 1 kind alone or a mixed solvent in which 2 or more kinds are combined.

For example, when the compound (a12) or the compound (a13) is a compound having a low fluorine atom content (the ratio of fluorine atoms in the molecular weight of the compound molecule), the solvent is not particularly limited as long as it is a solvent inactive to the reaction. Among the solvents inactive to the reaction, ether solvents such as diethyl ether, tetrahydrofuran and dioxane are preferred, and tetrahydrofuran is more preferred.

When the compound (a12) or the compound (a13) is a compound having a high fluorine atom content, a mixed solvent of the ether solvent and the fluorine solvent is preferably used.

Examples of the fluorine-based solvent include hydrofluorocarbons (e.g., 1H, 4H-perfluorobutane, 1H-perfluorohexane, 1H-tridecafluorohexane (AC-2000), 1,1,1,3, 3-pentafluorobutane, 1,1,2,2,3,3, 4-heptafluorocyclopentane, 2H, 3H-perfluoropentane, etc.), hydrochlorofluorocarbons (e.g., 3, 3-dichloro-1, 1,1,2, 2-pentafluoropropane, 1, 3-dichloro-1, 1,2,2, 3-pentafluoropropane (HCFC-225 cb)), hydrofluoroethers (CF-s) (e.g., CF-S), etc₃CH₂OCF₂CF₂H (AE-3000), 1,1,1,2,2,3,3,4,4,5,5,6, 6-tridecafluorooctane (AC-6000), (perfluorobutoxy) methane, (perfluorobutoxy) ethane, etc.), hydrochlorofluoroolefins ((Z) -1-chloro-2, 3,3,4,4,5, 5-heptafluoro-1-pentene (HCFO-1437dycc (Z) form, (E) -1-chloro-2, 3,3,4,4,5, 5-heptafluoro-1-pentene (HCFO-1437dycc (E)) form, (Z) -1-chloro-2, 3, 3-trifluoro-1-propene (HCFO-1233yd (Z)) form, (E) -1-chloro-2, 3, 3-trifluoro-1-propene (HCFO-1233yd (E)) form, etc.), Fluorine-containing aromatic compounds (perfluorobenzene, m-bis (trifluoromethyl) benzene (SR-Solvent), p-bis (trifluoromethyl) benzene, etc.), etc.

The reaction of reaction scheme (1) can be carried out, for example, by: a solution containing the compound (a12) or the compound (a13) is prepared, and after adding the transition metal compound and, if necessary, the ligand, a separately prepared solution of the compound (B2) is added.

The reaction temperature in the reaction scheme (2) may be, for example, from-20 ℃ to 66 ℃ (boiling point of tetrahydrofuran), and preferably from-20 ℃ to 40 ℃.

The composition containing a fluorine-containing compound of the present invention (hereinafter, also referred to as "the present composition") may contain the compound (a1) and the compound (a2), or may contain 1 or more selected from the compound (a1) and the compound (a2), and may contain another fluorine-containing ether compound. The present composition does not contain a liquid medium described later.

Examples of the other fluorine-containing ether compound include a fluorine-containing ether compound (hereinafter, also referred to as "fluorine-containing ether compound by-produced") by-produced in the production process of the present compound, a known fluorine-containing ether compound used for the same purpose as the present compound, and a fluorine-containing oil. As the other fluorine-containing compound, a compound which is less likely to degrade the characteristics of the present compound is preferable.

Examples of the fluorine-containing oil include Polytetrafluoroethylene (PTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), and Polychlorotrifluoroethylene (PCTFE).

As the by-product fluorine-containing compound, an unreacted fluorine-containing compound in the synthesis of the present compound and the like can be mentioned. When the present composition contains a fluorine-containing by-product, the purification step for removing the fluorine-containing by-product or reducing the amount of the fluorine-containing by-product can be simplified.

Examples of the known fluorine-containing compound include those described in the following documents.

Perfluoropolyether-modified aminosilane described in Japanese patent application laid-open No. 11-029585,

The silicon-containing organic fluorine-containing polymer described in Japanese patent No. 2874715,

An organosilicon compound described in Japanese patent laid-open publication No. 2000-144097,

Perfluoropolyether-modified aminosilane described in Japanese patent laid-open No. 2000-327772,

Fluorinated siloxane described in Japanese Kokai publication Hei-2002-506887,

An organosilicon compound described in Japanese patent application laid-open No. 2008-534696,

The fluorinated modified hydrogen-containing polymer described in Japanese patent No. 4138936,

The compounds described in U.S. patent application publication No. 2010/0129672, International publication No. 2014/126064, Japanese patent application laid-open No. 2014-070163,

The organosilicon compounds described in International publication Nos. 2011/060047 and 2011/059430,

A fluorine-containing organosilane compound described in International publication No. 2012/064649,

A fluorooxyalkylene group-containing polymer described in Japanese patent laid-open No. 2012-72272,

The fluorine-containing ether compounds described in International publication Nos. 2013/042732, 2013/121984, 2013/121985, 2013/121986, 2014/163004, JP-A2014-080473, 2015/087902, 2017/038830, 2017/038832 and 2017/187775,

Perfluoro (poly) ether-containing silane compounds described in Japanese patent laid-open Nos. 2014-218639, 2017/022437, 2018/079743 and 2018/143433,

Polymer-modified silane containing a fluorine-containing polyether group described in Japanese patent laid-open Nos. 2015-199906, 2016-204656, 2016-210854 and 2016-222859,

Examples of the fluorine-containing ether compound include those described in International publication No. 2018/216630, International publication No. 2019/039226, International publication No. 2019/039341, International publication No. 2019/039186, International publication No. 2019/044479, Japanese patent laid-open Nos. 2019 and 44158, and International publication No. 2019/163282.

Further, commercially available products of fluorine-containing compounds include KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by shin-Etsu chemical Co., Ltd., Afluid (registered trademark) S550 manufactured by AGC Co., Ltd., Optool (registered trademark) DSX manufactured by Daikin Industries, Ltd., Optool (registered trademark) AES, Optool (registered trademark) UF503, Optool (registered trademark) UD509, and the like.

The content of the present compound in the present composition is less than 100% by mass, preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more.

When the present composition contains another fluorine-containing compound, the proportion of the other fluorine-containing compound is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less, relative to the total amount of the present compound and the other fluorine-containing compound in the present composition.

The total ratio of the present compound and the other fluorine-containing compound in the present composition is preferably 80% by mass or more, more preferably 85% by mass or more.

When the content of the present compound and the other fluorine-containing compound is within the above range, the surface layer is excellent in water-and oil-repellency, abrasion resistance, fingerprint stain removability, lubricity, and appearance.

[ coating solution ]

The coating liquid of the present invention (hereinafter, also referred to as the present coating liquid) comprises the present compound or the present composition and a liquid medium. The coating liquid may be a liquid, solution or dispersion liquid.

The coating liquid may contain the present compound or the present composition, and may contain impurities such as by-products generated in the production process of the present compound.

The concentration of the present compound or the present composition in the present coating liquid is preferably 0.001 to 40% by mass, preferably 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass.

As the liquid medium, an organic solvent is preferable. The organic solvent may be a fluorine-containing organic solvent, a non-fluorine-containing organic solvent, or both.

Examples of the fluorine-containing organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.

The fluorinated alkane is preferably a C4-C8 compound. Examples of commercially available products include C₆F₁₃H (アサヒクリン (registered trademark) AC-2000, manufactured by AGC K.K.) and C₆F₁₃C₂H₅(アサヒクリン (registered trademark) AC-6000, manufactured by AGC K.K.) C₂F₅CHFCHFCF₃(manufactured by Chemours Company, Vertrel (registered trademark) XF).

Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis (trifluoromethyl) benzene.

The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms. Examples of commercially available products include CF₃CH₂OCF₂CF₂H (アサヒクリン (registered trademark) AE-3000, manufactured by AGC K.K.) and C₄F₉OCH₃(Novec (registered trademark) 7100, manufactured by 3M Co., Ltd.), C₄F₉OC₂H₅(Novec (registered trademark) 7200, manufactured by 3M Co., Ltd.), C₂F₅CF(OCH₃)C₃F₇(Novec (registered trademark) 7300, manufactured by 3M Co.).

Examples of the fluoroalkyl amine include perfluorotripropylamine and perfluorotributylamine.

Examples of the fluoroalcohol include 2,2,3, 3-tetrafluoropropanol, 2,2, 2-trifluoroethanol, hexafluoroisopropanol and the like.

The non-fluorine-containing organic solvent is preferably a compound composed of only hydrogen atoms and carbon atoms, or a compound composed of only hydrogen atoms, carbon atoms and oxygen atoms, and examples thereof include hydrocarbon-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, ether-based organic solvents, and ester-based organic solvents.

The coating liquid preferably contains 75 to 99.999 mass% of a liquid medium, preferably 85 to 99.99 mass% of a liquid medium, and particularly preferably 90 to 99.9 mass% of a liquid medium.

The coating liquid may contain other components than the present compound or the present composition and a liquid medium within a range not impairing the effects of the present invention.

Examples of the other component include known additives such as an acid catalyst and a basic catalyst which promote hydrolysis and condensation reactions of the hydrolyzable silyl group.

The content of other components in the coating liquid is preferably 10% by mass or less, more preferably 1% by mass or less.

The total concentration of the present compound and other components or the total concentration of the present composition and other components (hereinafter, also referred to as solid content concentration) in the present coating liquid is preferably 0.001 to 40% by mass, preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and still more preferably 0.01 to 1% by mass. The solid content concentration of the coating liquid is a value calculated from the mass of the coating liquid before heating and the mass after heating for 4 hours in a convection dryer at 120 ℃.

[ article ]

The article of the present invention (hereinafter, also referred to as "the present article") has a surface layer formed of the present compound or the present composition on the surface of a substrate. The surface layer may be formed on a part of the surface of the substrate or may be formed on the entire surface of the substrate. The surface layer may be spread in a film form on the surface of the substrate or may be dispersed in a dot form.

The surface layer contains the compound in a state in which a part or all of the hydrolyzable silyl groups of the compound undergo hydrolysis reaction and silanol groups undergo dehydration condensation reaction.

The thickness of the surface layer is preferably 1 to 100nm, particularly preferably 1 to 50 nm. When the thickness of the surface layer is 1nm or more, the effect by the surface treatment can be easily obtained sufficiently. When the thickness of the surface layer is 100nm or less, the utilization efficiency is high. The thickness of the surface layer can be calculated as follows: an interference pattern of reflected X-rays was obtained by an X-ray diffractometer for thin film analysis (ATX-G, manufactured by RIGAKU corporation) according to an X-ray reflectance method, and calculated from the oscillation period of the interference pattern.

Examples of the substrate include substrates to which water-and oil-repellency is required to be imparted. For example, there may be mentioned a base material used by being brought into contact with another article (for example, a stylus pen) or a human finger, a base material held by a human finger in some cases during operation, and a base material placed on another article (for example, a mounting table) in some cases.

Examples of the material of the substrate include metal, resin, glass, sapphire, ceramic, stone, and a composite material thereof. The glass may be chemically strengthened. SiO can be formed on the surface of the substrate₂A base film such as a film.

As the substrate, a substrate for a touch panel, a substrate for a display, and a spectacle lens are preferable, and a substrate for a touch panel is particularly preferable. As a material of the substrate for a touch panel, glass or a transparent resin is preferable.

Further, as the substrate, a glass or a resin film used for an exterior part (excluding a display part) in a device such as a mobile phone (for example, a smartphone), a portable information terminal (for example, a tablet terminal), a game machine, or a remote controller is also preferable.

[ method for producing article ]

The present article can be produced, for example, by the following method.

A method of treating the surface of the substrate by a dry coating method using the present compound or the present composition to form a surface layer made of the present compound or the present composition on the surface of the substrate.

A method of applying the present coating liquid to the surface of the substrate by a wet coating method, and drying the coating liquid to form a surface layer made of the present compound or the present composition on the surface of the substrate.

Examples of the dry coating method include vacuum deposition, CVD, sputtering, and the like. As the dry coating method, a vacuum deposition method is preferable in terms of suppressing decomposition of the compound 1A or the compound 1B and in terms of simplicity of the apparatus. In the case of vacuum deposition, a granular material obtained by impregnating a porous metal body such as iron or steel with the present compound or the present composition can be used. A granular material impregnated with compound 1A or compound 1B or the present composition can be used by impregnating a metal porous body such as iron or steel with the present coating liquid and drying the liquid medium.

Examples of the wet coating method include spin coating, wipe coating, spray coating, blade coating, dip coating, die coating, ink jet coating, flow coating, roll coating, casting, Langmuir-Blodgett method, and gravure coating.

In order to improve the rubbing resistance of the surface layer, an operation for promoting the reaction of the present compound with the base material may be performed as necessary. Examples of such operations include heating, humidification, and light irradiation.

For example, the substrate having the surface layer formed thereon is heated in an atmosphere having moisture, and a hydrolysis reaction of a hydrolyzable group, a reaction of a hydroxyl group or the like on the surface of the substrate with a silanol group, a formation of a siloxane bond by a condensation reaction of the silanol group, or the like can be promoted.

After the surface treatment, other compounds that are compounds in the surface layer, and compounds that do not chemically bond to the base material may be removed as necessary. Specific examples of the method include: a method of pouring a solvent on the surface layer; a method of wiping with a cloth impregnated with a solvent; and the like.

Examples

The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to these examples. In the following, "%" is "% by mass" unless otherwise specified. Examples 1 to 11, 13 to 33, and 35 to 41 are examples, and examples 12 and 34 are comparative examples.

The weight average molecular weight (Mw)/number average molecular weight (Mn) was determined by GPC (gel permeation chromatography) under the following conditions.

The device comprises the following steps: HLC-8420GPC (manufactured by Tosoh corporation)

Mobile phase: mixed solvent of 1, 3-bis (trifluoromethyl) benzene and acetone (80: 20 (volume ratio))

And (3) analyzing the column: PLgel3 μm MIXED-E (manufactured by Agilent Technologies Co., Ltd.)

Molecular weight measurement standard sample: 3 kinds of perfluoropolyethers having Mw/Mn of 1.2 or less and Mn of 2000 to 10000

Flow rate of mobile phase: 1.0 mL/min

Sample concentration: 10mg/mL

Column temperature: 40 deg.C

A detector: evaporative light scattering detector

Synthetic example 1: synthesis of Compound (1-1)

The following compound (1-1) was obtained according to the method described in example 7 of International publication No. 2013/121984.

CF₃-O-(CF₂CF₂O-CF₂CF₂CF₂CF₂O)_n(CF₂CF₂O)-CF₂CF₂CF₂-CH₂OH. formula (1-1)

The average value of the number n of repeating units was 13.

[ Synthesis example 2: synthesis of Compound (1-2)

The aforementioned compound (1-1) (6.80g), 2, 6-lutidine (0.759g), and AE-3000(28.0g) were added thereto, and the mixture was stirred at 0 ℃. After trifluoromethanesulfonic anhydride (0.987g) was added, stirring was performed at room temperature. After washing with water, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 6.81g of the following compound (1-2).

CF₃-O-(CF₂CF₂O-CF₂CF₂CF₂CF₂O)_n(CF₂CF₂O)-CF₂CF₂CF₂-CH₂OTf. formula (1-2)

The average number of repeating units n is 13, OTf is triflate: -O-S (═ O)₂(-CF₃)。

NMR spectrum of Compound (1-2);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 4.78(t, J ═ 12.3Hz, 2H).

¹⁹F-NMR (376MHz, deuterated chloroform) delta (ppm): -55.28, -74.11, -82.86, -88.07, -90.20, -119.84, -125.28, -126.16.

[ Synthesis example 3: synthesis of Compound (B-1)

Diethyl diallylmalonate (60.0g), lithium chloride (23.7g), water (6.45g) and dimethyl sulfoxide (263g) were added to stir at 160 ℃. After cooling to room temperature, water was added and extracted with ethyl acetate. Hexane was added to the organic layer, which was washed with saturated brine and dried over sodium sulfate. After filtration, the solvent was distilled off to obtain 39.5g of the following compound (B-1).

NMR spectrum of Compound (B-1);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): (ddt, J ═ 17.1, 10.1, 7.0Hz, 2H), 5.06-4.94 (m, 4H), 4.09(q, J ═ 7.1Hz, 2H), 2.47(ddd, J ═ 14.0, 8.0, 6.1Hz, 1H), 2.33(dt, J ═ 14.9, 7.5Hz, 2H), 2.22(dt, J ═ 14.1, 6.5Hz, 2H), 1.21(t, J ═ 7.1Hz, 3H).

[ Synthesis example 4: synthesis of Compound (B-2)

After addition of Tetrahydrofuran (THF) (260mL), diisopropylamine (29.8g), the solution was cooled to-78 ℃. An n-butyllithium hexane solution (2.76M, 96.6mL) was added, and the temperature was raised to 0 ℃. After stirring, it was cooled to-78 ℃ to prepare a solution of Lithium Diisopropylamide (LDA) in THF. To a THF solution was added the above-mentioned compound (B-1) (39.5g) and stirred, followed by addition of allyl bromide (24.1 mL). The temperature was raised to 0 ℃ and 1M hydrochloric acid (100mL) was added to distill off THF under reduced pressure. After extraction with dichloromethane, sodium sulfate was added. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 45.0g of compound (B-2).

NMR spectrum of Compound (B-2);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.74-5.62 (m, 3H), 5.04(dd, J ═ 13.6, 1.9Hz, 6H), 4.10(q, J ═ 7.1Hz, 2H), 2.29(d, J ═ 7.4Hz, 6H), 1.22(t, J ═ 7.1Hz, 3H).

[ Synthesis example 5: synthesis of Compound (B-3)

The above-mentioned compound (B-2) (45.0g) was dissolved in THF (620mL) and cooled to 0 ℃. Lithium aluminum hydride in THF (104mL) was added and stirred. Water and a 15% aqueous solution of sodium hydroxide were added thereto, and the mixture was stirred at room temperature and then diluted with dichloromethane. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 31.3g of the following compound (B-3).

NMR spectrum of Compound (B-3);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.90-5.76 (m, 3H), 5.10-5.02 (m, 6H), 3.38(s, 2H), 2.03(dt, J ═ 7.5, 1.2Hz, 6H), 1.45(s, 1H).

[ example 1: synthesis of Compound (B1-1)

Acetonitrile (380mL), the above-mentioned compound (B-3) (31.3g), triphenylphosphine (64.3g) and carbon tetrachloride (33.9g) were added thereto, and the mixture was stirred at 90 ℃. After concentration, ethyl acetate/hexane was added and stirred. After filtration and concentration, 28.2g of the following compound (B1-1) was obtained by distillation.

NMR spectrum of Compound (B1-1);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.83-5.67 (m, 3H), 5.16-5.01 (m, 6H), 3.32(s, 2H), 2.05(dt, J ═ 7.5, 1.1Hz, 6H).

[ example 2: synthesis of Compound (B2-1)

THF (35mL) and iodine (0.180g) were added to magnesium (2.36g), and the mixture was stirred at room temperature. A solution of the aforementioned compound (B1-1) (14.0g) in THF (35mL) was added, and the mixture was refluxed for 2 hours to prepare a solution (0.80M) of the following compound (B2-1).

[ example 3: synthesis of Compound (B1-2)

Adding 1-bromo-3-chloropropaneAlkane (2.90g), 1-phenyl-1-propyne (0.220g), CuCl₂(0.051g), stirring was carried out at 0 ℃. The aforementioned compound (B2-1) (0.80M, 26.0mL) was added thereto and stirred. 1M hydrochloric acid was added, extraction was performed with dichloromethane, and sodium sulfate was added. After filtration and concentration, 3.29g of the following compound (B1-2) was obtained by distillation.

NMR spectrum of Compound (B1-2);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.76(ddt, J ═ 16.6, 10.6, 7.4Hz, 3H), 5.09 to 4.93(m, 6H), 3.50(t, J ═ 6.7Hz, 2H), 1.96(dt, J ═ 7.4, 1.2Hz, 6H), 1.76 to 1.61(m, 2H), 1.45 to 1.29(m, 2H), 1.24 to 1.08(m, 2H).

[ example 4: synthesis of Compound (B2-2)

THF (2.6mL) and iodine (12.7mg) were added to magnesium (0.174g), and the mixture was stirred at room temperature. A solution (1.0M) of the following compound (B2-2) was prepared by adding a solution of the aforementioned compound (B1-2) (1.30g) in THF (2.6mL) and refluxing with heating.

[ Synthesis example 6: synthesis of Compound (1-3)

Adding CuCl₂(7.0mg), 1-phenyl-1-propyne (0.026g), 1, 3-bistrifluoromethylbenzene (23mL), the compound (1-2) (1.52g), and the compound (B2-2) (4.5mL, 1.0M) were added. After stirring at room temperature, the mixture was washed with 1M hydrochloric acid and dried over sodium sulfate. After filtration, the solvent was distilled off and AC-6000 was added. After washing with N, N-Dimethylformamide (DMF), flash column chromatography using silica gel was carried out to obtain 0.210g of the following compound (1-3).

Compound (1-3)

NMR spectrum of Compound (1-3);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.80(ddt, J ═ 20.3, 9.3, 7.4Hz, 3H), 5.01(dd, J ═ 13.5, 1.7Hz, 6H), 2.13 to 2.01(m, 2H), 1.97(d, J ═ 7.5Hz, 6H), 1.67 to 1.55(m, 2H), 1.40 to 1.27(m, 4H), 1.27 to 1.18(m, 2H).

¹⁹F-NMR (376MHz, deuterated chloroform) delta (ppm): -55.25, -82.83, -88.06, -90.16(d, J ═ 8.1Hz), -114.18, -125.26, -126.59.

[ example 5: synthesis of Compound (I)

To the mixture were added AC-2000(1.2g), the above-mentioned compound (1-3) (0.200g), a xylene solution of platinum/1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex (platinum content: 2%, 7.0mg), aniline (1.5mg), and trimethoxysilane (32.2mg), and the mixture was stirred at 40 ℃ for 18 hours, and then the solvent was distilled off under reduced pressure to obtain 0.201g of a fluorine-containing ether compound (I) shown below. The Mw/Mn of Compound (I) determined by the GPC method was 1.07.

Compound (I)

Average of repeating units (n 1): 13

NMR spectrum of Compound (I);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 3.59(s, 27H), 2.15 to 1.91(m, 2H), 1.72 to 1.54(m, 2H), 1.52 to 1.14(m, 18H), 0.73 to 0.60(m, 6H).

¹⁹F-NMR (376MHz, deuterated chloroform) delta (ppm): -55.28, -82.30(d, J ═ 22.0Hz), -82.88, -88.10, -90.22, -114.17, -125.30, -126.49.

[ example 6: synthesis of Compound (B1-3)

1-bromo-4-chlorobutane (2.89g), 1-phenyl-1-propyne (0.198g), and CuCl were added₂(0.049g) was stirred at 0 ℃. The aforementioned compound (B2-1) was added(0.80M, 24.0mL) and stirred. 1M hydrochloric acid was added, extraction was performed with dichloromethane, and sodium sulfate was added. After filtration and concentration, 3.45g of the following compound (B1-3) was obtained by distillation.

NMR spectrum of Compound (B1-3);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.76(ddt, J ═ 16.8, 10.4, 7.4Hz, 3H), 5.07 to 4.92(m, 6H), 3.49(t, J ═ 6.8Hz, 2H), 1.94(dt, J ═ 7.4, 1.2Hz, 6H), 1.79 to 1.67(m, 2H), 1.42 to 1.30(m, 2H), 1.30 to 1.20(m, 2H), 1.20 to 1.10(m, 2H).

[ example 7: synthesis of Compound (B2-3)

THF (2.6mL) and iodine (14.0mg) were added to magnesium (0.168g), and the mixture was stirred at room temperature. A solution of the aforementioned compound (B1-3) (1.41g) in THF (2.6mL) was added, and the mixture was refluxed for 2 hours to prepare a solution (0.74M) of the following compound (B2-3).

[ Synthesis example 7: synthesis of Compound (2-1)

Adding CuCl₂(9.9mg), 1-phenyl-1-propyne (0.019g), 1, 3-bistrifluoromethylbenzene (23mL), the above-mentioned compound (1-2) (1.50g), and the above-mentioned compound (B2-3) (4.5mL, 1.0M) were added thereto. After stirring at room temperature, the mixture was washed with 1M hydrochloric acid and dried over sodium sulfate. After filtration, the solvent was distilled off and AC-6000 was added. After washing with DMF and MeOH, flash column chromatography was performed using silica gel to obtain 0.246g of the following compound (2-1).

Compound (2-1)

NMR spectrum of Compound (2-1);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.90 to 5.73(m, 3H), 5.13 to 4.91(m, 6H), 2.14 to 2.01(m, 2H), 1.97(d, J ═ 7.4Hz, 6H), 1.69 to 1.52(m, 2H), 1.47 to 1.18(m, 8H).

¹⁹F-NMR (376MHz, deuterated chloroform) delta (ppm): -55.23, -82.35(dt, J ═ 22.8, 10.3Hz), -82.81, -87.93, -90.15(d, J ═ 8.4Hz), -114.19, -125.23, -126.58.

[ example 8: synthesis of Compound (II)

To the mixture were added AC-2000(1.5g), the above-mentioned compound (2-1) (0.246g), a xylene solution of platinum/1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex (platinum content: 2%, 8.9mg), aniline (1.3mg), and trimethoxysilane (26.9mg), and the mixture was stirred at 40 ℃ and then the solvent was distilled off under reduced pressure to obtain 0.252g of the fluorine-containing ether compound (II) shown below. The Mw/Mn of the compound (II) determined by the GPC method was 1.06.

Compound (II)

Average of repeating units (n 2): 14

NMR spectrum of compound (II);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 3.60(s, 27H), 2.14-1.95 (m, 2H), 1.66-1.54 (m, 2H), 1.52-1.16 (m, 20H), 0.75-0.61 (m, 6H).

¹⁹F-NMR (376MHz, deuterated chloroform) delta (ppm): -55.28, -82.33, -82.86, -88.08, -90.18, -114.24, -125.29, -126.51.

[ example 9: synthesis of Compound (B1-4)

1-bromo-5-chlorobutane (2.89g), 1-phenyl-1-propyne (0.182g), and CuCl were added₂(0.042g) was stirred at 0 ℃. The aforementioned compound (B2-1) (0.80M, 21.5mL) was added and stirred for 1 hour. 1M hydrochloric acid was added, extraction was performed with dichloromethane, and sodium sulfate was added. Filtering, concentrating, performing flash column chromatography with silica gel,thus, 2.95g of the following compound (B1-4) was obtained.

NMR spectrum of Compound (B1-4);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.83 to 5.68(m, 3H), 5.06 to 4.94(m, 6H), 3.49(t, J-6.8 Hz, 2H), 1.94(dt, J-7.4, 1.2Hz, 6H), 1.80 to 1.65(m, 2H), 1.46 to 1.32(m, 2H), 1.28 to 1.09(m, 6H).

[ example 10: synthesis of Compound (B2-4)

THF (2.6mL) and iodine (21.8mg) were added to magnesium (0.172g), and the mixture was stirred at room temperature. A solution of the aforementioned compound (B1-4) (1.47g) in THF (2.6mL) was added, and the mixture was refluxed for 2 hours to prepare a solution (0.99M) of the following compound (B2-4).

[ Synthesis example 8: synthesis of Compound (3-1)

Adding CuCl₂(7.0mg), 1-phenyl-1-propyne (0.026g), 1, 3-bistrifluoromethylbenzene (24mL), the compound (1-2) (1.51g), and the compound (B2-4) (4.8mL, 0.99M) were added. After stirring at room temperature, the mixture was washed with 1M hydrochloric acid and dried over sodium sulfate. After filtration, the solvent was distilled off, washed with hexane, and subjected to flash column chromatography using silica gel to obtain 0.213g of the following compound (3-1).

Compound (3-1)

NMR spectrum of Compound (3-1);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.87 to 5.72(m, 3H), 5.07 to 4.93(m, 6H), 2.12 to 1.99(m, 2H), 1.97(d, J ═ 7.5Hz, 6H),1.64～1.53(m，2H)，1.41～1.17(m，10H).

¹⁹F-NMR (376MHz, deuterated chloroform) delta (ppm): -55.22, -82.77, -87.95(d, J ═ 39.1Hz), -90.12(d, J ═ 8.5Hz), -114.15, -125.19, -126.55.

[ example 11: synthesis of Compound (III)

To the mixture were added AC-2000(1.3g), the above-mentioned compound (1-7) (0.213g), a xylene solution of platinum/1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex (platinum content: 2%, 7.4mg), aniline (2.2mg), and trimethoxysilane (45.9mg), and the mixture was stirred at 40 ℃ and then the solvent was distilled off under reduced pressure to obtain 0.225g of the fluorine-containing ether compound (III) shown below. The Mw/Mn of the compound (III) determined by the GPC method was 1.07.

Compound (III)

Average of repeating units (n 3): 13

NMR spectrum of compound (III);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 3.60(s, 27H), 2.15-1.94 (m, 2H), 1.66-1.54 (m, 2H), 1.54-1.13 (m, 22H), 0.75-0.61 (m, 6H).

¹⁹F-NMR (376MHz, deuterated chloroform) delta (ppm): -55.26, -82.32(dt, J ═ 23.2, 10.6Hz), -82.84, -88.07, -90.17(d, J ═ 8.6Hz), -114.18, -125.24(d, J ═ 16.1Hz), -126.51.

[ example 12: synthesis of Compound (IV)

The following compound (IV) was obtained according to the method described in example 7 of International publication No. 2017/038830.

CF₃-O-(CF₂CF₂O-CF₂CF₂CF₂CF₂O)_n4(CF₂CF₂O)-CF₂CF₂CF₂-CH₂OCH₂-C{CH₂CH₂CH₂Si(OMe)₃)}₃The formula (IV)

The average value of the number of repeating units n4 was 13.

[ Synthesis example 9: synthesis of Compound (5-1)

Adding CuCl₂(16.0mg), 1-phenyl-1-propyne (0.052g), 1, 3-bistrifluoromethylbenzene (24mL), the above-mentioned compound (1-2) (4.00g), and then the above-mentioned compound (B2-1) (5.0mL, 1.0M) were added. After stirring at room temperature, the mixture was washed with 1M hydrochloric acid and dried over sodium sulfate. After filtration, the solvent was distilled off and AC-6000 was added. After washing with MeOH, flash column chromatography using silica gel was performed to obtain 0.139g of the following compound (5-1).

Compound (5-1)

Average of repeating units (n 5): 10

NMR spectrum of Compound (5-1);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.77(ddt, J ═ 14.9, 10.7, 7.4Hz, 3H), 5.07 to 4.99(m, 6H), 2.19 to 2.05(m, 2H), 1.97(d, J ═ 7.4Hz, 6H), 1.59 to 1.50(m, 2H).

¹⁹F-NMR (376MHz, deuterated chloroform) delta (ppm): -55.29, -82.90, -88.13, -90.24(d, J ═ 8.0Hz), -114.62, -125.34, -126.49.

[ example 13: synthesis of Compound (V)

AC-2000(0.89g), the above-mentioned compound (5-1) (0.139g), a xylene solution of platinum/1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex (platinum content: 2%, 5.5mg), aniline (0.8mg), and trimethoxysilane (22.7mg) were added thereto, and the mixture was stirred at 40 ℃ and then the solvent was distilled off under reduced pressure to obtain 0.145g of the following fluorine-containing ether compound (V). The Mw/Mn of the compound (V) determined by the GPC method was 1.07.

Compound (V)

Average of repeating units (n 5): 10

NMR spectrum of compound (V);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 3.60(s, 27H), 2.23 to 1.95(m, 2H), 1.63 to 1.28(m, 14H), 0.67(t, J ═ 7.6Hz, 6H).

¹⁹F-NMR (376MHz, deuterated chloroform) delta (ppm): -55.33, -82.95, -88.17, -90.13, -90.40(m), -114.07-114.32 (m), -125.38, -126.04.

[ example 14: synthesis of Compound (B1-5)

THF (33mL), the above-mentioned compound (B-3) (1.66g), triphenylphosphine (2.88g) and carbon tetrabromide (3.64g) were added to the solution, and the mixture was stirred at 10 ℃. Hexane (30mL) was added, and the mixture was filtered, concentrated and distilled to obtain 1.06g of the following compound (B1-5).

NMR spectrum of Compound (B1-5);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.74(ddt, J ═ 16.7, 10.5, 7.5Hz, 3H), 5.18 to 5.01(m, 6H), 3.24(s, 2H), 2.06(dt, J ═ 7.5, 1.1Hz, 6H).

The same procedures as in example 2, synthesis example 9 and synthesis example 13 were carried out except that the compound (B1-5) was used in place of the compound (B1-1), thereby confirming that the compound (V) could be synthesized.

[ Synthesis example 10: synthesis of Compound (B-4)

After paraformaldehyde (0.489g) and THF (9.5mL) were added, the above-mentioned compound (B2-1) (20mL, 0.9M) was added. After stirring at room temperature, 1M hydrochloric acid was added. After extraction with dichloromethane, it is dried over sodium sulfate. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 1.98g of the following compound (OH compound).

NMR spectrum of Compound (B-4);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.80(ddt, J-16.8, 10.4, 7.4Hz, 3H), 5.14-4.91 (m, 6H), 3.74-3.60 (m, 2H), 1.99(dt, J-7.4, 1.2Hz, 6H), 1.61-1.45 (m, 2H).

[ example 15: synthesis of Compound (B1-6)

Acetonitrile (22mL), the above-mentioned compound (2-3) (1.98g), triphenylphosphine (3.75g) and carbon tetrachloride (2.00g) were added thereto, and the mixture was stirred at 90 ℃. After concentration, ethyl acetate/hexane was added and stirred. After filtration and concentration, flash column chromatography using silica gel was performed to obtain 1.73g of the following compound (B1-6).

NMR spectrum of Compound (B1-6);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.84-5.69 (m, 3H), 5.12-4.98 (m, 6H), 3.55-3.46 (m, 2H), 1.98(dt, J ═ 7.4, 1.2Hz, 6H), 1.76-1.68 (m, 2H).

[ example 16: synthesis of Compound (B2-6)

THF (1.3mL) and iodine (9.0mg) were added to magnesium (0.099g), and the mixture was stirred at room temperature. A solution of the aforementioned compound (B1-6) (0.570g) in THF (1.3mL) was added to the solution, and the mixture was refluxed with heating to prepare a solution (1.0M) of the following compound (B2-6).

[ Synthesis example 11: synthesis of Compound (6-1)

Adding CuCl₂(4.0mg), 1-phenyl-1-propyne (0.116g), 1, 3-bistrifluoromethylbenzene (10mL), the above-mentioned compound (1-2) (1.01g), and then the above-mentioned compound (B2-6) (1.6mL, 1.0M) were added. Stirring at room temperatureAfter that, it was washed with 1M hydrochloric acid and dried over sodium sulfate. After filtration, the solvent was distilled off and AC-6000 was added. After washing with MeOH, flash column chromatography using silica gel was performed to obtain 0.110g of the following compound (6-1).

Compound (6-1)

Average of repeating units (n 6): 11

NMR spectrum of Compound (6-1);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.85 to 5.71(m, 3H), 5.07 to 4.94(m, 6H), 2.04 to 1.78(m, 8H), 1.64 to 1.38(m, 2H), 1.32 to 1.05(m, 2H).

¹⁹F-NMR (376MHz, deuterated chloroform) delta (ppm): -55.28, -82.40, -82.86, -88.09, -90.20(d, J ═ 9.6Hz), -114.25, -125.29, -126.55.

[ example 17: synthesis of Compound (VI)

To the mixture were added AC-2000(0.89g), the above-mentioned compound (6-1) (0.110g), a xylene solution of platinum/1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex (platinum content: 2%, 5.3mg), aniline (0.9mg), and trimethoxysilane (22.7mg), and the mixture was stirred at 40 ℃ and then the solvent was distilled off under reduced pressure to obtain 0.109g of the following fluorine-containing ether compound (VI). Mw/Mn of the compound (VI) determined by the GPC method was 1.08.

Compound (VI)

Average of repeating units (n 6): 11

NMR spectrum of compound (VI);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 3.58(s, 27H), 2.23-1.98 (m, 2H), 1.64-1.20 (m, 16H), 0.79-0.58 (m, 6H).

¹⁹F-NMR(376MHz, deuterated chloroform) δ (ppm): -55.28, -82.90, -88.13, -90.11, -90.30(m), -114.01-114.29 (m), -125.31, -125.99.

[ example 18: synthesis of Compound (B1-7)

THF (44mL), the above-mentioned compound (B-3) (4.00g), triphenylphosphine (7.64g) and carbon tetrabromide (8.66g) were added to stir at 0 ℃. Hexane (10mL) was added, and after filtration and concentration, flash column chromatography using silica gel was performed to obtain 3.36g of the following compound (B1-7).

NMR spectrum of Compound (B1-7);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.79(ddt, J is 16.8, 10.2, 7.4Hz, 3H), 5.18-4.98 (m, 6H), 3.48-3.29 (m, 2H), 2.05-1.93 (m, 6H), 1.89-1.78 (m, 2H).

The same procedures as in example 16, synthesis example 11 and synthesis example 17 were carried out except that the compound (B1-7) was used in place of the compound (B1-6), thereby confirming that the compound (VI) could be synthesized.

[ example 19: synthesis of Compound (B1-8)

1-bromo-2-chloroethane (2.90g), 1-phenyl-1-propyne (0.235g), and CuCl were added₂(0.055g), and stirring was performed at 0 ℃. The aforementioned compound (B2-1) (0.97M, 7.0mL) was added thereto, and the mixture was stirred for 1 hour. 1M hydrochloric acid was added, extraction was performed with dichloromethane, and sodium sulfate was added. After filtration and concentration, 2.32g of the following compound (B1-8) was obtained by distillation.

NMR spectrum of Compound (B1-8);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.77(ddt, J ═ 16.8, 10.4, 7.4Hz, 3H), 5.07 to 4.96(m, 6H), 3.45(t, J ═ 6.7Hz, 2H), 1.96(dt, J ═ 7.4,1.2Hz，6H)，1.78～1.65(m，2H)，1.33～1.24(m，2H).

[ example 20: synthesis of Compound (B2-8)

THF (2.6mL) and iodine (0.013g) were added to magnesium (0.174g), and the mixture was stirred at room temperature. A solution of the aforementioned compound (B1-8) (1.21g) in THF (2.6mL) was added to the solution, and the mixture was refluxed with heating to prepare a solution (1.0M) of the following compound (B2-8).

[ Synthesis example 12: synthesis of Compound (7-1)

Adding CuCl₂(6.4mg), 1-phenyl-1-propyne (0.018g), 1, 3-bistrifluoromethylbenzene (23mL), the above-mentioned compound (1-2) (1.50g), and the above-mentioned compound (B2-8) (4.5mL, 1.0M) were added thereto. After stirring at room temperature, the mixture was washed with 1M hydrochloric acid and dried over sodium sulfate. After filtration, the solvent was distilled off and AC-6000 was added. After washing with MeOH, flash column chromatography using silica gel was performed to obtain 0.126g of the following compound (7-1).

Compound (7-1)

Average of repeating units (n 7): 12

NMR spectrum of Compound (7-1);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.87 to 5.68(m, 3H), 5.06 to 4.92(m, 6H), 2.16 to 1.92(m, 8H), 1.62 to 1.50(m, 2H), 1.41 to 1.34(m, 2H), 1.28 to 1.19(m, 2H)

¹⁹F-NMR (376MHz, deuterated chloroform) delta (ppm): -55.23, -82.33, -82.78, -88.02, -90.15, -114.17, -125.21, -126.55.

[ example 21: synthesis of Compound (VII)

To the mixture were added AC-2000(0.89g), the above-mentioned compound (7-1) (0.126g), a xylene solution of platinum/1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex (platinum content: 2%, 5.5mg), aniline (1.8mg), and trimethoxysilane (22.7mg), and the mixture was stirred at 40 ℃ and then the solvent was distilled off under reduced pressure to obtain 0.111g of the following fluorine-containing ether compound (VII). The Mw/Mn of compound (VII) determined by the GPC method was 1.07.

Compound (VII)

Average of repeating units (n 7): 12

NMR spectrum of compound (VII);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 3.59(s, 27H), 2.18 to 1.93(m, 2H), 1.70 to 1.19(m, 18H), 0.77 to 0.61(m, 6H).

¹⁹F-NMR (376MHz, deuterated chloroform) delta (ppm): -55.28, -82.60(d, J ═ 22.0Hz), -82.78, -88.11, -90.21, -114.11, -125.32, -126.11.

[ Synthesis example 13: synthesis of Compound (8-1)

FLUOROLINK D4000(Solvay Specialty Polymers Co., Ltd. (4.03g), 2, 6-lutidine (0.759g), AE-3000(28.0g) were added thereto, and the mixture was stirred at 0 ℃. After trifluoromethanesulfonic anhydride (0.987g) was added, stirring was performed at room temperature. After washing with water, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 3.56g of the following compound (8-1).

Compound (8-1)

Where, average of p 8: 22, average of q 8: 25

NMR spectrum of Compound (8-1);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 4.89(q, J ═ 8.4Hz, 1H).

Synthesis example 14: synthesis of Compound (8-2)

Adding CuCl₂(7.0mg), 1-phenyl-1-propyne (0.026g), 1, 3-bistrifluoromethylbenzene (15mL), the above-mentioned compound (8-1) (1.62g), and the above-mentioned compound (B1-2) (4.0mL, 1.0M) were added. After stirring at room temperature, the mixture was washed with 1M hydrochloric acid and dried over sodium sulfate. After filtration, the solvent was distilled off and AC-6000 was added. After washing with methanol, flash column chromatography using silica gel was performed to obtain 0.201g of the following compound (8-2).

Compound (8-2)

Where, average of p 8: 22, average of q 8: 25

NMR spectrum of Compound (8-2);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.90 to 5.66(m, 6H), 5.07 to 4.90(m, 12H), 2.19 to 1.92(m, 16H), 1.70 to 1.10(m, 16H).

[ example 21: synthesis of Compound (VIII)

To the mixture were added AC-2000(1.2g), the above-mentioned compound (8-2) (0.201g), a xylene solution of platinum/1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex (platinum content: 2%, 7.0mg), aniline (1.4mg), and trimethoxysilane (51.7mg), and the mixture was stirred at 40 ℃ for 18 hours, and then the solvent was distilled off under reduced pressure to obtain 0.188g of the fluorine-containing ether compound (VIII) described below. The Mw/Mn of compound (VIII) determined by the GPC method was 1.11.

Compound (VIII)

Where, average of p 8: 22, average of q 8: 25

NMR spectrum of compound (VIII);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 3.61(s, 54H), 2.17-1.90 (m, 4H), 1.70-1.14 (m, 40H), 0.74-0.59 (m, 12H).

[ Synthesis example 15: synthesis of Compound (9-1)

The following compound (9-1) was synthesized according to the method described in examples 1 to 6 of International publication No. 2017/038830.

CF₃CF₂CF₂-O-(CF₂CF₂O)(CF₂CF₂O){(CF₂O)_p9(CF₂CF₂O)_q9}-CF₂-CH₂OSO₂CF₃The formula (9-1)

Where, average of p 9: 22, average of q 9: 24

Synthesis example 16: synthesis of Compound (9-2)

Adding CuCl₂(7.0mg), 1-phenyl-1-propyne (0.026g), 1, 3-bistrifluoromethylbenzene (15mL), the above-mentioned compound (9-1) (4.03g), and the above-mentioned compound (B1-2) (4.0mL, 1.0M) were added thereto. After stirring overnight at 50 ℃, it was washed with 1M hydrochloric acid and dried over sodium sulfate. After filtration, the solvent was distilled off and AC-6000 was added. After washing with methanol, flash column chromatography using silica gel was performed to obtain 0.246g of the following compound (9-2).

Compound (9-2)

Where, average of p 9: 22, average of q 9: 24

NMR spectrum of Compound (9-2);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.88 to 5.67(m, 3H), 5.06 to 4.90(m, 6H), 2.20 to 1.91(m, 8H), 1.71 to 1.07(m, 8H).

[ example 22: synthesis of Compound (IX) ]

To the mixture were added AC-2000(1.5g), the above-mentioned compound (9-2) (0.246g), a xylene solution of platinum/1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex (platinum content: 2%, 3.9mg), aniline (1.1mg), and trimethoxysilane (24.4mg), and the mixture was stirred at 40 ℃ for 18 hours, followed by distilling off the solvent under reduced pressure to obtain 0.244g of the fluorine-containing ether compound (IX) described below. Mw/Mn of compound (IX) determined by the GPC method was 1.10.

Compound (IX)

Where, average of p 9: 22, average of q 9: 24

NMR spectrum of compound (IX);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 3.60(s, 27H), 2.18 to 1.91(m, 2H), 1.71 to 1.14(m, 20H), 0.73 to 0.60(m, 6H).

[ Synthesis example 17: synthesis of Compound (B-5)

After addition of THF (20mL), diisopropylamine (4.2mL), the solution was cooled to-78 ℃. An n-butyllithium hexane solution (2.76M, 9.9mL) was added, and the temperature was raised to 0 ℃. After stirring, it was cooled to-78 ℃ to prepare a solution of Lithium Diisopropylamide (LDA) in THF. After the above-mentioned compound (B-1) (4.00g) was added to a THF solution and stirred, 4-bromo-1-butene (3.85g) was added thereto and stirred at room temperature overnight. After cooling to 0 ℃, 1M hydrochloric acid (30mL) was added and THF was distilled off under reduced pressure. After extraction with dichloromethane, sodium sulfate was added. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 4.01g of compound (B-5).

NMR spectrum of Compound (B-5);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.84 to 5.60(m, 3H), 5.11 to 5.03(m, 4H), 4.99(dq, J ═ 17.1, 1.6Hz, 1H), 4.92(ddt, J ═ 10.1, 2.0, 1.2Hz, 1H), 4.13(q, J ═ 7.1Hz, 2H), 2.40 to 2.26(m, 4H), 2.01 to 1.90(m, 2H), 1.65 to 1.58(m, 2H), 1.24(t, J ═ 7.1Hz, 3H).

[ Synthesis example 18: synthesis of Compound (B-6)

The above-mentioned compound (B-5) (4.01g) was dissolved in THF (40mL) and cooled to 0 ℃. A THF solution of lithium aluminum hydride (27mL) was added and stirred at 40 ℃. Water and a 15% aqueous solution of sodium hydroxide were added thereto, and the mixture was stirred at room temperature. After filtration, the solvent was distilled off to obtain 2.41g of the following compound (B-6).

NMR spectrum of Compound (B-5);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.91-5.71 (m, 3H), 5.14-5.04 (m, 4H), 5.01(dq, J ═ 17.1, 1.6Hz, 1H), 4.92(ddt, J ═ 10.1, 2.2, 1.2Hz, 1H), 3.40(d, J ═ 6.2Hz, 2H), 2.07-2.00 (m, 6H), 1.37-1.31 (m, 2H).

[ example 23: synthesis of Compound (B1-9)

Acetonitrile (7mL), the above-mentioned compound (B-6) (2.30g), triphenylphosphine (3.61g) and carbon tetrachloride (1.87g) were added thereto, and the mixture was stirred at 90 ℃. After concentration, ethyl acetate/hexane was added and stirred. After filtration and concentration, 1.85g of the following compound (B1-9) was obtained by distillation.

NMR spectrum of Compound (B1-9);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.87 to 5.66(m, 3H), 5.15 to 5.06(m, 4H), 5.01(dq, J ═ 17.1, 1.7Hz, 1H), 4.94(ddt, J ═ 10.1, 1.9, 1.2Hz, 1H), 3.35(s, 2H), 2.11 to 1.98(m, 6H), 1.42 to 1.31(m, 2H).

[ example 24: synthesis of Compound (B2-9)

THF (3.8mL) and iodine (0.031g) were added to magnesium (0.182g), and the mixture was stirred at room temperature. A solution of the aforementioned compound (B1-9) (1.12g) in THF (3.8mL) was added, and the mixture was refluxed for 2 hours to prepare a solution (0.8M) of the following compound (B2-9).

[ Synthesis example 19: synthesis of Compound (10-1)

Adding CuCl₂(16.0mg), 1-phenyl-1-propyne (0.04g), 1, 3-bistrifluoromethylbenzene (17mL), the above-mentioned compound (1-2) (4.02g), and the above-mentioned compound (B2-9) (4.3mL, 0.8M) were added thereto. After stirring at 50 ℃, the mixture was washed with 1M hydrochloric acid and dried over sodium sulfate. After filtration, the solvent was distilled off and AC-6000 was added. After washing with MeOH, flash column chromatography using silica gel was performed to obtain 0.35g of the following compound (10-1).

Compound (10-1)

Average of repeating units (n 10): 11

NMR spectrum of Compound (B1-9);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.84 to 5.66(m, 3H), 5.12 to 4.81(m, 6H), 2.19 to 1.90(m, 8H), 1.60 to 1.51(m, 2H), 1.33 to 1.26(m, 2H).

¹⁹F-NMR (376MHz, deuterated chloroform) delta (ppm): -55.09(t, J ═ 9.1Hz), -81.95 to-82.21 (m), -82.59, -87.4 to-88.17 (m), -89.96(q, J ═ 9.0Hz), -114.25, -124.99, and-126.19.

[ example 25: synthesis of Compound (X)

To the mixture were added AC-2000(1.55g), the above-mentioned compound (10-1) (0.257g), a xylene solution of platinum/1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex (platinum content: 2%, 9.9mg), aniline (7.4mg), and trimethoxysilane (36.8mg), and the mixture was stirred at 40 ℃ and then the solvent was distilled off under reduced pressure to obtain 0.253g of the following fluorine-containing ether compound (X). The Mw/Mn of the compound (X) determined by the GPC method was 1.06.

Compound (X)

Average of repeating units (n 10): 11

NMR spectrum of compound (X);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 3.59(d, J ═ 2.0Hz, 27H), 2.19 to 1.98(m, 2H), 1.62 to 1.20(m, 16H), 0.77 to 0.58(m, 6H).

¹⁹F-NMR (376MHz, deuterated chloroform) delta (ppm): -55.08(t, J ═ 9.2Hz), -81.77 to-82.86 (m), -87.43 to-88.18 (m), -89.81 to-90.18 (m), -113.67 to-114.24 (m), -124.67 to-125.10 (m), -125.81

[ example 26: synthesis of Compound (B1-10)

Acetonitrile (60mL), 1, 6-heptadien-4-ol (10.0g), triphenylphosphine (30.6g) and carbon tetrachloride (16.0g) were added thereto, and the mixture was stirred at 90 ℃. After completion of the reaction, 1.86g of the compound (B1-10) was obtained by distillation.

NMR spectrum of Compound (B1-10);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.84(ddt, J ═ 17.6, 9.7, 6.9Hz, 2H), 5.18 to 5.05(m, 4H), 3.94(tt, J ═ 7.4, 5.4Hz, 1H), 2.59 to 2.36(m, 4H).

[ example 27: synthesis of Compound (B2-10)

THF (6.5mL) and iodine (36.0mg) were added to magnesium (0.424g), and the mixture was stirred at room temperature. A solution (0.86M) of the following compound (B2-10) was prepared by adding a solution of the aforementioned compound (B1-10) (1.86g) in THF (6.5mL) and refluxing with heating.

[ example 28: synthesis of Compound (B1-11)

1-bromo-3-chloropropane (1.60g) and 1-phenyl-1-propyne were added(0.118g)、CuCl₂(0.027g), stirring was carried out at 0 ℃. The aforementioned compound (B2-10) (0.86M, 14.0mL) was added and stirred. 1M hydrochloric acid was added, extraction was performed with dichloromethane, and sodium sulfate was added. After filtration and concentration, flash column chromatography using silica gel was performed. Further distillation was carried out to obtain 1.28g of compound (B1-11).

NMR spectrum of Compound (B1-11);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.84-5.66 (m, 2H), 5.09-4.96 (m, 4H), 3.51(t, J ═ 6.8Hz, 2H), 2.15-2.01 (m, 4H), 1.86-1.71 (m, 2H), 1.59-1.47 (m, 1H), 1.45-1.35 (m, 2H).

[ example 29: synthesis of Compound (B2-11)

THF (4.5mL) and iodine (39.0mg) were added to magnesium (0.211g), and the mixture was stirred at room temperature. A solution of the aforementioned compound (B1-11) (1.20g) in THF (4.5mL) was added to the solution, and the mixture was refluxed with heating to prepare a solution (0.63M) of the following compound (B2-11).

[ Synthesis example 20: synthesis of Compound (11-1)

Adding CuCl₂(27.0mg), 1-phenyl-1-propyne (0.070g), 1, 3-bistrifluoromethylbenzene (29mL), the above-mentioned compound (1-2) (4.30g), and then the above-mentioned compound (B2-11) (9.5mL, 0.63M) were added. After stirring at room temperature, the mixture was washed with 1M hydrochloric acid and dried over sodium sulfate. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 0.266g of the following compound (11-1).

Compound (11-1)

Average value (n) of repeating units: 13

[ example 30: synthesis of Compound (XI)

To the mixture were added AC-2000(1.55g), the above-mentioned compound (11-1) (0.257g), a xylene solution of platinum/1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex (platinum content: 2%, 9.9mg), aniline (7.4mg), and trimethoxysilane (36.8mg), and the mixture was stirred at 40 ℃ and then the solvent was distilled off under reduced pressure to obtain 0.253g of the following fluorine-containing ether compound (XI). Mw/Mn of compound (XI) determined by the GPC method was 1.07.

Compound (XI)

Average value (n) of repeating units: 13

NMR spectrum of compound (XI);

¹H-NMR (400MHz, deuterated chloroform) delta (ppm): 5.72(ddt, J ═ 17.3, 10.2, 7.1Hz, 2H), 5.06-4.84 (m, 4H), 2.18-1.88 (m, 6H), 1.66-1.14 (m, 7H).

¹⁹F-NMR (376MHz, deuterated chloroform) delta (ppm): -56.65(t, J ═ 9.2Hz), -83.60 to-83.81 (m), -84.14, -89.06 to-89.69 (m), -91.50(q, J ═ 9.0Hz), -115.54, -126.56, -127.97.

[ examples 31 to 41: production and evaluation of articles

The substrates were subjected to surface treatment using the above-mentioned compounds I to XI, to obtain articles of examples 31 to 41. For each example, the following dry coating method and wet coating method were used as the surface treatment method. Chemically tempered glass is used as a substrate. The obtained article was evaluated by the following method. The results are shown in Table 1.

(Dry coating method)

The dry coating was performed using a vacuum deposition apparatus (VTR 350M, manufactured by ULVAC corporation) (vacuum deposition method). 0.5g of each compound was charged into a molybdenum boat in a vacuum deposition apparatus, and the vacuum deposition apparatus was evacuated to 1X 10^-3Pa or less. Will be matched withThe boat containing the compound was heated at a temperature rise rate of 10 ℃/min or less, and the shutter was opened at a time when the deposition rate based on the crystal oscillation film thickness exceeded 1 nm/sec, to start film deposition onto the surface of the substrate. The shutter was closed at the time when the film thickness became about 50nm, and the deposition onto the surface of the substrate was completed. The substrate on which the compound was deposited was subjected to heat treatment at 200 ℃ for 30 minutes and washed with dichloropentafluoropropane (AK-225, manufactured by AGC Co., Ltd.) to obtain an article having a surface layer on the surface of the substrate.

(Wet coating method)

Each compound was reacted with C as a medium₄F₉OC₂H₅(Novec (registered trademark) 7200, manufactured by 3M Co.) was mixed to prepare a coating solution having a solid content of 0.05%. The substrate was immersed in the coating liquid, left to stand for 30 minutes, and then pulled up (dip coating method).

The coating film was dried at 200 ℃ for 30 minutes and washed with AK-225 to obtain an article having a surface layer on the surface of the substrate.

(evaluation method)

< method for measuring contact Angle >

The contact angle of about 2. mu.L of distilled water or n-hexadecane placed on the surface of the surface layer was measured by a contact angle measuring apparatus (DM-500, manufactured by Kyowa Kagaku Co., Ltd.). The measurement was performed at 5 different positions in the surface of the surface layer, and the average value thereof was calculated. For the calculation of the contact angle, the 2 θ method was used.

< initial contact Angle >

For the surface layer, the initial water contact angle and the initial n-hexadecane contact angle were measured by the aforementioned measurement methods. The evaluation criteria are as follows.

Initial water contact angle of the fluorine-containing ether compound represented by formula (a 1):

good (good): over 115 degrees.

X (not): below 115 degrees.

Initial water contact angle of the fluorine-containing ether compound represented by formula (a 2):

good (good): over 115 degrees.

Δ (optional): 105 degrees or more and less than 115 degrees.

X (not): below 105 degrees.

< Friction resistance (Steel wool) >

For the surface layer, according to JIS L0849: 2013(ISO 105-X12: 2001), steel wool Bonster (#0000) was subjected to a reciprocating traverse test (KNT Co., Ltd.) under a pressure of: 98.07kPa, speed: after 1 ten thousand reciprocations at 320 cm/min, the water contact angle was determined according to the method described above. The smaller the decrease in water repellency (water contact angle) after rubbing, the smaller the decrease in performance due to rubbing, and the more excellent the rub resistance. The evaluation criteria are as follows.

Good (good): the change in water contact angle after 1 ten thousand cycles of reciprocation was 5 degrees or less.

X (not): the change of the water contact angle after 1 ten thousand cycles exceeds 5 degrees.

< light resistance >

For the surface layer, a benchtop xenon arc lamp type accelerated light resistance tester (product name: SUNTEST XLS +, manufactured by toyo seiki co., ltd.) was used, and the temperature of the black panel: irradiating at 63 deg.C with light (650W/m)²300 to 700nm) for 500 hours, the water contact angle is determined according to the method described above. The evaluation criteria are as follows.

Good (good): the change in water contact angle after the accelerated light resistance test is 5 degrees or less.

X (not): the change in water contact angle after the accelerated light resistance test exceeds 5 degrees.

[ Table 1]

TABLE 1

As shown in table 1, although the initial contact angle was good for compound IV, the decrease in water contact angle was confirmed after the rubbing test and after the light resistance test. On the other hand, it is shown that: the fluorine-containing ether compounds I to III and V to XI having no ether bond (-C-O-C-) in the linking group can suppress the decrease in water contact angle even after the rubbing test and the light resistance test, and have excellent durability.

The present application claims priority based on the japanese application special application 2019-171550, filed on 2019, month 9 and day 20, the disclosure of which is hereby incorporated in its entirety.

Claims

1. A fluorine-containing ether compound represented by the following formula (A1) or formula (A2),

R^f-O-(R^f1O)_m-R^f2[-R¹-C(-R²-T)_a(-R³)_3-a]_bformula (A1)

Wherein the content of the first and second substances,

R^fis a fluoroalkyl group having 1 to 20 carbon atoms,

R^f1a C1-C6 fluoroalkylene group,

t is-Si (R)_3-c(L)_cAnd a plurality of T are optionally the same or different,

r is an alkyl group, and R is a substituted alkyl group,

m is an integer of 1 to 20,

c is 2 or 3, a plurality of c are optionally the same or different,

when b is 1, a is 2 or 3.

2. The fluoroether compound of claim 1, wherein R's are more than one²All of the carbon numbers of (2) are 3 or more.

3. The fluorine-containing ether compound according to claim 1 or 2, wherein R is¹The number of carbon atoms of (2) is 5 to 20.

4. The fluorine-containing ether compound according to any one of claims 1 to 3, wherein-CH₂-in an amount of 8 to 30.

5. The fluorine-containing ether compound according to any one of claims 1 to 4, which has a weight average molecular weight (Mw)/number average molecular weight (Mn) of 1.2 or less.

6. The fluorine-containing ether compound according to any one of claims 1 to 5, wherein the hydrolyzable group is an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, or an isocyanate group.

7. A surface treating agent comprising the compound according to any one of claims 1 to 6.

8. A fluoroether composition comprising: a fluorine-containing ether compound represented by the following formula (A1) and a fluorine-containing ether compound represented by the following formula (A2),

R^f-O-(R^f1O)_m-R^f2[-R¹-C(-R²-T)_a(-R³)_3-a]_bformula (A1)

Wherein the content of the first and second substances,

R^fis a fluoroalkyl group having 1 to 20 carbon atoms,

R^f1a C1-C6 fluoroalkylene group,

R²is C2-10 alkylene optionally having fluorine atom, multiple R²Optionally the same or different, and optionally,

t is-Si (R)_3-c(L)_cAnd a plurality of T are optionally the same or different,

r is an alkyl group, and R is a substituted alkyl group,

m is an integer of 1 to 20,

c is 2 or 3, a plurality of c are optionally the same or different,

when b is 1, a is 2 or 3.

9. A fluoroether composition comprising: 1 or more of the fluorine-containing ether compound according to any one of claims 1 to 6, and other fluorine-containing ether compounds.

10. A coating liquid comprising the fluorine-containing ether compound according to any one of claims 1 to 6 or the fluorine-containing ether composition according to claim 8 or 9,

and contains a liquid medium.

11. An article having a surface layer formed of the fluorine-containing ether compound according to any one of claims 1 to 6 or the fluorine-containing ether composition according to claim 8 or 9 on the surface of a substrate.

12. A compound represented by the following formula (B1),

(CH₂＝CH-R²⁰-)_a(R³-)_3-aC-R²¹-X formula (B1)

Wherein the content of the first and second substances,

R²¹a single bond or an alkylene group having 1 to 19 carbon atoms,

x is a chlorine atom, a bromine atom, or an iodine atom,

a is an integer of 1 to 3.

13. A compound represented by the following formula (B2),

(CH₂＝CH-R²⁰-)_a(R³-)_3-aC-R²¹-MgX formula (B2)

Wherein the content of the first and second substances,

R²⁰is a single bond or C1-C8 alkylene optionally having a fluorine atom, R²⁰When there are plural, the plural R²⁰Optionally the same or different, in the presence of a surfactant,

R²¹is a single bond or an alkylene group having 1 to 19 carbon atomsThe base group is a group of a compound,

x is a chlorine atom, a bromine atom, or an iodine atom,

a is an integer of 1 to 3.